Polymerization of diallyl esters and products thereof



Po it? F b, 1

lTED STATES OFFICE POLYMERIZA'HON OI DIALLYL EST! I! PRODUCTS THEREOF Theodore E'Bradley. Stamford, Oonm. aasignor to American Cyanamid Company. New York, N. Y., a corporation oi Maine No Drawing. Original application April 1. 1987.

Serial No..18l,8l7. Divided and this application September 26, 1989, Serial No. 390,61!

Claims. (0]. 260-") may be obtained by combining chemically various polybaslc acids and polyhydric alcohols. with or without the use oi various modifying agents. These polyesters are generally referred to as being of the alkyd resin type and. where they are heat convertible. the ilnal products may be somewhat lacking in water and alkali-resistance. narily these alkyd resins are colored by unavoidable impurlties and it is seldom possible to obtain resins or esters approaching the more desirable water-white color.

It is also true that many monohydric alcohols have been combined with various acids, includins poiycarboxyllc acids. but the esters so obtained are not convertible. In other words. these esters. when heated. generally distil or decompose without being polymerized to an iniusible and insoluble form. Esters such as cellulose acetate. polyvinyl acetate. the polymethyl and polyethyl esters of acrylic and methacrylic acids and the like are generally water-white and have relatively good water and alkali-resistance. but these materials likewise do not have the property oi being converted to the insoluble and iniusible form upon heating. This property is essential for the production oi most heat resistant coatings, as well as for the more rigid and resistant type oi molding or casting resins.

I have found that I can prepare polymerized esters having many interesting and unique characteristics which permit of their use in novel combinations and compositions. I have especially found that I may prepare polymers of thecompound. diallyl iurnarate. and the following are illustrations of the principles and practice of my invention which is not limited to the speciilc examples given.

trample 1 I add 40 parts by weight or i'umaryl chloride slowly to parts by weight of allyl alcohol. The mixture is allowed to react at room temperature and under anhydrous conditions. After the reaction has proceeded to a sumcient degree. the excess alcohol and hydrogen chloride are removed ing ester remaining is amber-colored and in order to obtain a substantially colorless produot.'it is Ordifractionated under reduced pressure and there is obtained a 78% yield oi water-white diailyl iumarate boiling at -115 C. at 7 millimeters pressure. The acid number is 3.1. saponiilcation number m, refractive index. 1.407! at 80' O. and

the density 1.068 at L CI 15 This liquid ester undergoes spontaneous pelymeri nation at room temperatures during a period or.

several months. iorining a rubber-like. waterwhite, solid gel comprising a mixturaoi unpolymerised and polymerized terms of the ester. ultimate polymer is a hard. water-white, amorphous substance which is iniusible and is also 111-. soluble in the various common organic solvents. The polymer is highly water and alkali-resistant and cannot be saponiiledbythe usual methods to yield the alkali salt oi iumaric acid.

ThQ P lymerization of diallyl iumarate was observed to be greatly accelerated by catalysts such as peroxides, from 0.1% to 1.6% oi benaoyl peroxide being especially elloctive for this purpose. polymerisation isaccelerated at elevated temperatures. requiring irjom elite Ob -min. at C. in the absence oi added catalyst, but only 15 to 30 min. at luv-12s O. in the presence oi from 0.1 to 1.596 oi bensoyl peroxide.

For the production oi coating compositions it is best to polymerize the diallyl iumarate (or its equivalent) only partially so that while of increased viscosity it is still quite largely soluble in organic solvents. These solutions may then be applied as coatings and then force dried to the converted term at an elevated temperature. In such cases it has usually been iound desirable to conduct the polymerization in the presence oi a suitable catalyst.

The partially polymerized solution may also be blended with other film-forming agents as ior example alkyd resins, bodied oils, alkylated or other hydrocarbon-soluble terms of the ureaiorlnaldehyde and phenol-formaldehyde resins.

cellulose esters or others and similar compatible materials. In many such cases these blends are more compatible and elleotive. and products of superior physical characteristics are obtained by eilecting chemical reactions between the diverse polymers or their monomers rather than by merely relying upon physical blends. This is especially true of the copolymers of these esters with the upon gentle heating under vacuum. .The result- 5 drying oils and/or the alkyd type resins. particu- The larlythosemodiiiedwithdryingoilsordryingoil acidsorboth.

By polymerization of the pure esters or of their 1 mixtures with other unsaturated bodies under suitable conditions, as in plaster oiParis or lead.

molds and the like,'there are obtained lightcolored or water-white castings oi the insoluble Example 2 .Diallvl schemata-20 parts by weight sebacyl chloride were heated with 9.8 parts by weight allyl alcohol. A vigorous reaction occurred at the beginning. When this reaction died down, the reaction mixture was heated in a water bath yielding a faint yellow liquid. When heated in the presence of the crystal oi! benaoyl peroxide, a soft, plastic, flexible gel resulted. When leit exposed in sunlight for '12 hours and to the direct light oi an ultra violet lamp for 3 hours, no change occurred provided no peroxide was present.

. Example 3 Dilzllylsuocinate-lbb parts byweight of succinyl chloride were added to 11.6 parts by weight allyl alcohol. The reaction was carried out as above. The product produced was a water-white liquid, stable to sunlight'and ultra violet light. When boiled with aluminum chloride, a gel resulted which was plastic in nature but not as flexible as the gel produced irom diallyl sebacate. No reaction occurred when diallyl succinate was heated with tin tetrachloride. When heated in 45 the presence of benzoyl peroxide, a gel formed with the characteristics already described for the diallyl sebacate.

Example l Didllfll phthalate-One mol of phthalyl ch10 ridewasreactedwith2molsallyl alcohol. The resulting product was a crystalline solid. 'lhe solid when heated in the presence or benaoyl peroxide as a catalyst produced a mixture or brittie. elled material'and some ungelled crystals.

Allortheesterspreparedinaccordancewith Examples 2, 3 and 4 maybe purified in the same manner as describedin Example 1 to obtain products which give better gels than the crude products or the examples. It will be obvious that other means or preparing my esters may be utilized and suitable com-. binations oi my esters with other materials may be prepared. Any other desired changes may be adopted without departing from the spirit and scope or m'y'invention as deiined in the appended claims.-

I claim:

1. A composition or matter consisting oi insoluble and iniusible polymerized diallyl ester of a polycarboxylic acid selected irom the group consisting of iumaric acid, sebacic acid. succinic acid, adipic acid and phthalic acid.

. 2. A composition oi! matter consisting of polymerized diallyl iumarate, said iumarate being a substantially iniusible and insoluble solid.

3. A process or preparing a resinous polymer which comprises heating, until there is produced a substantially insoluble. and iniusible solid, a

composition having diallyl rumarate as its sole polymerizable component and containing a poly- -merlzation catalyst.

4. A process of preparing a resinous polymer which comprises heating for about 15-30 minutes at a temperature of about -125 C. until there is produced a substantially insoluble and infusible solid, a composition including a polymerization catalyst and having as its sole polymerizable component an ester selected from the group consisting oiv diallyl iumarate, diallyl sebacate, diallyl succinate, diallyl adipate and diallyl phthalate.

5. A composition of matter consistingoi insoluble and iniusible polymerized diallyl phthalate.

THEODORE 1. BRADLEY. 

